Potassium-ion batteries(KIBs)have great potential for applications in large-scale energy storage devices.However,the larger radius of K+leads to sluggish kinetics and inferior cycling performance,severely restricting ...Potassium-ion batteries(KIBs)have great potential for applications in large-scale energy storage devices.However,the larger radius of K+leads to sluggish kinetics and inferior cycling performance,severely restricting its practical applicability.Herein,we propose a rational strategy involving a Prussian blue analogue-derived graphitized carbon anode with fast and durable potassium storage capability,which is constructed by encapsulating cobalt nanoparticles in nitrogen-doped graphitized carbon(Co-NC).Both experimental and theoretical results show that N-doping effectively promotes the uniform dispersion of cobalt nanoparticles in the carbon matrix through Co-N bonds.Moreover,the cobalt nanoparticles and strong Co-N bonds synergistically form a threedimensional conductive network,increase the number of adsorption sites,and reduce the diffusion energy barrier,thereby facilitating the adsorption and the diffusion kinetics.These multiple effects lead to enhanced reversible capacities of 305 and 208.6 mAh g^−1 after 100 and 300 cycles at 0.05 and 0.1 A g^−1,respectively,demonstrating the applicability of the Co-NC anode for KIBs.展开更多
Alcohol fuel electro-reforming is promising for green hydrogen generation while developing efficient bifunctional catalysts for alcohol fuel electrolysis is still very tricky.Herein,we for the first time proposed the ...Alcohol fuel electro-reforming is promising for green hydrogen generation while developing efficient bifunctional catalysts for alcohol fuel electrolysis is still very tricky.Herein,we for the first time proposed the electron-enriched Pt induced by CoSe_(2)has an efficient bi-functional catalytic ability for alcohol fuels electro-reforming of hydrogen in acid electrolytes.The theoretical calculation revealed the advantages of electron-enriched Pt surface for the adsorption of intermediate,which is well supported by spectroscopic analysis and CO-stripping techniques.Largely improved catalytic performances of activity,durability,and kinetics are demonstrated compared to the conventional alloy system and commercial Pt/C catalyst,due to the efficient synergism of Pt and CoSe_(2);the peak current density of Pt/CoSe_(2)for methanol(ethanol)oxidation is 87.61(48.27)m A cm^(-2),which is about 3.3(2.0)times higher than that of Pt/C catalyst and 2.0(1.5)times that of the traditional PtCo alloy catalysts.Impressively,about 80%of the initial current was found after 1000 cycles of stability test for alcohol fuel oxidation of Pt/CoSe_(2)catalyst,higher than that of Pt/C(ca.50%)and PtCo catalyst(65%).When Pt/CoSe_(2)catalyst serviced as bi-functional catalysts for electrolyzer,a low cell potential of 0.65(0.78)V for methanol(ethanol)electrolysis was required to reach 10 m A cm^(-2),which was about 1030(900)m V less than that of conventional water electrolysis using Pt/C as the catalyst.The current result is instructive for the design of novel bifunctional catalyst and the understanding of hydrogen generation via alcohol fuel electro-reforming.展开更多
An efficient sustainable and scalable strategy for the synthesis of porous cobalt/nitrogen co-doped carbons(Co@NCs) via pyrolysis of aniline-modified ZIFs,has been demonstrated.Aniline can coordinate and absorb on the...An efficient sustainable and scalable strategy for the synthesis of porous cobalt/nitrogen co-doped carbons(Co@NCs) via pyrolysis of aniline-modified ZIFs,has been demonstrated.Aniline can coordinate and absorb on the surface of ZIF(ZIF-CoZn3-PhA),accelerate the precipitation of ZIFs,thus resulting in smaller ZIF particle size.Meanwhile,the aniline on the surface of ZIF-CoZn3-PhA promotes the formation of the protective carbon shell and smaller Co nanoparticles,and increases nitrogen content of the catalyst.Because of these prope rties of Co@NC-PhA-3,the oxidative esterification of 5-hydroxymethylfurfural can be carried out under ambient conditions.According to our experimental and computational results,a synergistic catalytic effect between CoNx sites and Co nanoparticles has been established,in which both Co nanoparticles and CoNx can activate O2 while Co nanoparticles bind and oxidize HMF.Moreover,the formation and release of active oxygen species in CoNx sites are reinfo rced by the electronic interaction between Co nanoparticles and CoNx.展开更多
Developing high performance and cost-effective electrocatalysts toward oxygen reduction reaction(ORR)is of critical significance for fuel cells and metal–air batteries.Herein,CoO@Co nanoparticles encapsulated in thre...Developing high performance and cost-effective electrocatalysts toward oxygen reduction reaction(ORR)is of critical significance for fuel cells and metal–air batteries.Herein,CoO@Co nanoparticles encapsulated in three-dimensional(3D)porous nitrogen-doped carbon(CoO@Co/Co-N-C)have been successfully derived from the cobalt–tannin framework via the NH4Cl salt template strategy.Owing to the generated NH3 and HCl gas from NH4Cl during the pyrolysis process,CoO@Co/Co-N-C formed a 3D porous carbon architecture with ultrahigh-specific surface area(1052.5 m^(2)g^(-1)).This hybrid catalyst exhibits comparable ORR catalytic activity,as well as superior stability to 20 wt%Pt/C in alkaline conditions.This finding offers a novel and facile strategy to synthesize 3D porous carbon as non-precious metal electrocatalysts for energy conversion and storage applications.展开更多
In this contribution, a comparative study of metallic cobalt micro and nanoparticles obtained in solution by four different chemical routes is reported. Classic routes such as borohydride reduction in aqueous media an...In this contribution, a comparative study of metallic cobalt micro and nanoparticles obtained in solution by four different chemical routes is reported. Classic routes such as borohydride reduction in aqueous media and the so-called polyol methodology were used to obtain the cobalt nanostructures to be studied. Using CTAB as surfactant, cobalt hollow nanostructures were obtained. The use of strong reducing agents, like sodium borohydride, favors the formation of quasi-monodispersed nanoparticles of about 2 nm size but accompanied with impurities; for hydrazine(a mild reducer), nanoparticles of larger size are obtained which organize in spherical microagglomerates. Valuable information on the particles thermal stability and on nature of the species anchored at their surface was obtained from thermogravimetric curves. The samples to be studied were characterized from UV-vis, IR, X-ray diffraction, and electron microscopy images(scanning and transmission).展开更多
Exploring highly active but inexpensive electrocatalysts for the hydrogen evolution reaction(HER)is of critical importance for hydrogen production from electrochemical water splitting.Herein,we report a multicomponent...Exploring highly active but inexpensive electrocatalysts for the hydrogen evolution reaction(HER)is of critical importance for hydrogen production from electrochemical water splitting.Herein,we report a multicomponent catalyst with exceptional activity and durability for HER,in which cobalt nanoparticles were in-situ confined inside bamboo-like carbon nanotubes(CNTs)while ultralow ruthenium loading(~2.6μg per electrode area~cm^(−2))is uniformly deposited on their exterior walls(Co@CNTsǀRu).The atomic-scale structural investigations and theoretical calculations indicate that the confined inner Co and loaded outer Ru would induce charge redistribution and a synergistic electron coupling,not only optimizing the adsorption energy of H intermediates(ΔGH*)but also facilitating the electron/mass transfer.The as-developed Co@CNTsǀRu composite catalyst requires overpotentials of only 10,32,and 63 mV to afford a current density of 10 mA cm^(−2) in alkaline,acidic and neutral media,respectively,representing top-level catalytic activity among all reported HER catalysts.The current work may open a new insight into the rational design of carbon-supported metal catalysts for practical applications.展开更多
采用溶胶-凝胶自蔓延燃烧法制备稀土Ce^(3+)掺杂纳米CoFe_2O_4,使用XRD、EDS、FT-IR、TEM和PNA等手段对产物的物相组成、形貌和电磁参数进行表征和分析,研究了掺杂稀土Ce^(3+)对纳米CoFe_2O_4的结构和吸波性能的影响。结果表明:所制备出...采用溶胶-凝胶自蔓延燃烧法制备稀土Ce^(3+)掺杂纳米CoFe_2O_4,使用XRD、EDS、FT-IR、TEM和PNA等手段对产物的物相组成、形貌和电磁参数进行表征和分析,研究了掺杂稀土Ce^(3+)对纳米CoFe_2O_4的结构和吸波性能的影响。结果表明:所制备出的CoFe_2O_4和CoFe_(1.7)Ce_(0.3)O_4具有尖晶石型结构,其粒径分别为70 nm和60 nm;在0~6 GHz频率范围内CoFe_(2-x)Ce_xO_4的吸波性能比纯CoFe_2O_4有了很大的提高,当x=0.3时吸波性能最佳,在5030 MHz处最大吸收峰值为-27.6 d B,-5 d B频宽为1.6GHz。展开更多
合成了一种石墨烯基纳米复合材料即:由氮掺杂碳层包覆的金属钴纳米颗粒,充分分散于氮掺杂的石墨烯表面。这种纳米复合材料进一步提高了石墨烯的导电性,增加了石墨烯的储锂容量。该材料被用作锂离子电池负极材料,在性能测试中展现了良好...合成了一种石墨烯基纳米复合材料即:由氮掺杂碳层包覆的金属钴纳米颗粒,充分分散于氮掺杂的石墨烯表面。这种纳米复合材料进一步提高了石墨烯的导电性,增加了石墨烯的储锂容量。该材料被用作锂离子电池负极材料,在性能测试中展现了良好的循环性能,在以100 m A·g-1的电流密度循环200圈后,放电容量高达950.1 m Ah·g-1,库伦效率约为98%。展开更多
基金supported by National Natural Science Foundation of China(Grant No.51932011,51802356)Innovation-Driven Project of Central South University(No.2020CX024)+3 种基金the Research Support Fund of the Collaborative Innovation Center of Manganese-Zinc-Vanadium Industrial Technology in Hunan Province(No.201809)the Program of Youth Talent Support for Hunan Province(2018RS3098)Hunan Provincial Innovation Foundation for Postgraduate(Grant No.CX2017B045)the Fundamental Research Funds for the Central Universities of Central South University(Grant No.2020zzts075).
文摘Potassium-ion batteries(KIBs)have great potential for applications in large-scale energy storage devices.However,the larger radius of K+leads to sluggish kinetics and inferior cycling performance,severely restricting its practical applicability.Herein,we propose a rational strategy involving a Prussian blue analogue-derived graphitized carbon anode with fast and durable potassium storage capability,which is constructed by encapsulating cobalt nanoparticles in nitrogen-doped graphitized carbon(Co-NC).Both experimental and theoretical results show that N-doping effectively promotes the uniform dispersion of cobalt nanoparticles in the carbon matrix through Co-N bonds.Moreover,the cobalt nanoparticles and strong Co-N bonds synergistically form a threedimensional conductive network,increase the number of adsorption sites,and reduce the diffusion energy barrier,thereby facilitating the adsorption and the diffusion kinetics.These multiple effects lead to enhanced reversible capacities of 305 and 208.6 mAh g^−1 after 100 and 300 cycles at 0.05 and 0.1 A g^−1,respectively,demonstrating the applicability of the Co-NC anode for KIBs.
基金supported by the National Natural Science Foundation of China(21972124,22102105)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutionthe support of the Six Talent Peaks Project of Jiangsu Province(XCL-070-2018)。
文摘Alcohol fuel electro-reforming is promising for green hydrogen generation while developing efficient bifunctional catalysts for alcohol fuel electrolysis is still very tricky.Herein,we for the first time proposed the electron-enriched Pt induced by CoSe_(2)has an efficient bi-functional catalytic ability for alcohol fuels electro-reforming of hydrogen in acid electrolytes.The theoretical calculation revealed the advantages of electron-enriched Pt surface for the adsorption of intermediate,which is well supported by spectroscopic analysis and CO-stripping techniques.Largely improved catalytic performances of activity,durability,and kinetics are demonstrated compared to the conventional alloy system and commercial Pt/C catalyst,due to the efficient synergism of Pt and CoSe_(2);the peak current density of Pt/CoSe_(2)for methanol(ethanol)oxidation is 87.61(48.27)m A cm^(-2),which is about 3.3(2.0)times higher than that of Pt/C catalyst and 2.0(1.5)times that of the traditional PtCo alloy catalysts.Impressively,about 80%of the initial current was found after 1000 cycles of stability test for alcohol fuel oxidation of Pt/CoSe_(2)catalyst,higher than that of Pt/C(ca.50%)and PtCo catalyst(65%).When Pt/CoSe_(2)catalyst serviced as bi-functional catalysts for electrolyzer,a low cell potential of 0.65(0.78)V for methanol(ethanol)electrolysis was required to reach 10 m A cm^(-2),which was about 1030(900)m V less than that of conventional water electrolysis using Pt/C as the catalyst.The current result is instructive for the design of novel bifunctional catalyst and the understanding of hydrogen generation via alcohol fuel electro-reforming.
基金the Fundamental Research Funds for the Central Universities (No.30920021120)Key Laboratory of Biomass Energy and Material,Jiangsu Province (No. JSBEM201912) for financial supporta project funded by the Priority Academic Program development of Jiangsu Higher Education Institution。
文摘An efficient sustainable and scalable strategy for the synthesis of porous cobalt/nitrogen co-doped carbons(Co@NCs) via pyrolysis of aniline-modified ZIFs,has been demonstrated.Aniline can coordinate and absorb on the surface of ZIF(ZIF-CoZn3-PhA),accelerate the precipitation of ZIFs,thus resulting in smaller ZIF particle size.Meanwhile,the aniline on the surface of ZIF-CoZn3-PhA promotes the formation of the protective carbon shell and smaller Co nanoparticles,and increases nitrogen content of the catalyst.Because of these prope rties of Co@NC-PhA-3,the oxidative esterification of 5-hydroxymethylfurfural can be carried out under ambient conditions.According to our experimental and computational results,a synergistic catalytic effect between CoNx sites and Co nanoparticles has been established,in which both Co nanoparticles and CoNx can activate O2 while Co nanoparticles bind and oxidize HMF.Moreover,the formation and release of active oxygen species in CoNx sites are reinfo rced by the electronic interaction between Co nanoparticles and CoNx.
基金supported by the National Natural Science Foundation of China(No.22202143)Suzhou Science and Technology planning project(No.SS202016)the USTS starting fund(No.332012104).
文摘Developing high performance and cost-effective electrocatalysts toward oxygen reduction reaction(ORR)is of critical significance for fuel cells and metal–air batteries.Herein,CoO@Co nanoparticles encapsulated in three-dimensional(3D)porous nitrogen-doped carbon(CoO@Co/Co-N-C)have been successfully derived from the cobalt–tannin framework via the NH4Cl salt template strategy.Owing to the generated NH3 and HCl gas from NH4Cl during the pyrolysis process,CoO@Co/Co-N-C formed a 3D porous carbon architecture with ultrahigh-specific surface area(1052.5 m^(2)g^(-1)).This hybrid catalyst exhibits comparable ORR catalytic activity,as well as superior stability to 20 wt%Pt/C in alkaline conditions.This finding offers a novel and facile strategy to synthesize 3D porous carbon as non-precious metal electrocatalysts for energy conversion and storage applications.
基金partially supported by the Consejo Nacional de Ciencia y Tecnología(CONACYTMéxico)under Grant SEP-CONACyT 2009No.129048
文摘In this contribution, a comparative study of metallic cobalt micro and nanoparticles obtained in solution by four different chemical routes is reported. Classic routes such as borohydride reduction in aqueous media and the so-called polyol methodology were used to obtain the cobalt nanostructures to be studied. Using CTAB as surfactant, cobalt hollow nanostructures were obtained. The use of strong reducing agents, like sodium borohydride, favors the formation of quasi-monodispersed nanoparticles of about 2 nm size but accompanied with impurities; for hydrazine(a mild reducer), nanoparticles of larger size are obtained which organize in spherical microagglomerates. Valuable information on the particles thermal stability and on nature of the species anchored at their surface was obtained from thermogravimetric curves. The samples to be studied were characterized from UV-vis, IR, X-ray diffraction, and electron microscopy images(scanning and transmission).
基金supported by“Shuguang Program”supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission Shaanxi Outstanding Youth Fund(2020JC-49)Youth Innovation Team of University in Shaanxi Province(20SG03)+2 种基金State Key Laboratory of New Textile Materials and Advanced Processing Technologies(No.FZ2021001)Guangdong Basic and Applied Basic Research Foundation(2021A1515110496)the Natural Science Basic Research Plan in Shaanxi Province of China(No.2022JQ-438).
文摘Exploring highly active but inexpensive electrocatalysts for the hydrogen evolution reaction(HER)is of critical importance for hydrogen production from electrochemical water splitting.Herein,we report a multicomponent catalyst with exceptional activity and durability for HER,in which cobalt nanoparticles were in-situ confined inside bamboo-like carbon nanotubes(CNTs)while ultralow ruthenium loading(~2.6μg per electrode area~cm^(−2))is uniformly deposited on their exterior walls(Co@CNTsǀRu).The atomic-scale structural investigations and theoretical calculations indicate that the confined inner Co and loaded outer Ru would induce charge redistribution and a synergistic electron coupling,not only optimizing the adsorption energy of H intermediates(ΔGH*)but also facilitating the electron/mass transfer.The as-developed Co@CNTsǀRu composite catalyst requires overpotentials of only 10,32,and 63 mV to afford a current density of 10 mA cm^(−2) in alkaline,acidic and neutral media,respectively,representing top-level catalytic activity among all reported HER catalysts.The current work may open a new insight into the rational design of carbon-supported metal catalysts for practical applications.
文摘采用溶胶-凝胶自蔓延燃烧法制备稀土Ce^(3+)掺杂纳米CoFe_2O_4,使用XRD、EDS、FT-IR、TEM和PNA等手段对产物的物相组成、形貌和电磁参数进行表征和分析,研究了掺杂稀土Ce^(3+)对纳米CoFe_2O_4的结构和吸波性能的影响。结果表明:所制备出的CoFe_2O_4和CoFe_(1.7)Ce_(0.3)O_4具有尖晶石型结构,其粒径分别为70 nm和60 nm;在0~6 GHz频率范围内CoFe_(2-x)Ce_xO_4的吸波性能比纯CoFe_2O_4有了很大的提高,当x=0.3时吸波性能最佳,在5030 MHz处最大吸收峰值为-27.6 d B,-5 d B频宽为1.6GHz。
文摘合成了一种石墨烯基纳米复合材料即:由氮掺杂碳层包覆的金属钴纳米颗粒,充分分散于氮掺杂的石墨烯表面。这种纳米复合材料进一步提高了石墨烯的导电性,增加了石墨烯的储锂容量。该材料被用作锂离子电池负极材料,在性能测试中展现了良好的循环性能,在以100 m A·g-1的电流密度循环200圈后,放电容量高达950.1 m Ah·g-1,库伦效率约为98%。
